CZ347395A3 - Polyolefin wax and process for preparing thereof - Google Patents

Abstract

Polypropylene (PP) wax is claimed, with a melt viscosity of 50-100,000 mPa.s at 170 degrees C, a DSC heat of fusion of less than 80 J/g, a DSC m.pt. of above 130 degrees C and a mol wt distribution (Mw/Mn) of less than 3. Also claimed is the prodn. of polyolefin wax with the above properties in the presence of a catalyst contg a metallocene cpd (A) and a cocatalyst (B), cpd (A) being present as a mixt of rac- and meso-forms with a rac/meso ratio of less than 0.5. Suitable metallocenes (A) include various diorganosilyl-bis(indenyl)zirconium cpds, eg dimethylsilyl-bis-(2-methyl-benzindenyl)-ZrCl2 (Al). Cocatalysts (B) are linear and/or cyclic aluminoxanes.

Description

(57) Polypropylene wax has a melt viscosity of 50 to 100000 mPa · s at 170 ° C, DSC melting point less than 80 J / g, DSC melting point greater than 130 ° C and molecular weight distribution Mw / Mn less than or equal to 3. Method of production This is waxed in the presence of a catalyst comprising a metallocene compound A and a cocatalyst B, wherein the metallocene compound A is used as a mixture of rac form and meso form in a ratio rac / meso = 0.5.

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Polyolefin wax and process for its production

Technical field

The present invention relates to a high melting point polyolefin wax, reduced isotaxis, reduced crystallinity and reduced hardness, as well as a process for its preparation.

BACKGROUND OF THE INVENTION

The production of polyolefin waxes with a broad molecular weight distribution Mw / Mn and an isotactic index of 60 to 80% using supported catalysts, cocatalysts and stereoregulators at temperatures above 95 ° C is known (see DE-A 31 48 229). However, large quantities of hydrogen must be used as molecular weight regulators in addition to high temperatures. The partial hydrogen pressure exceeds the olefin partial pressure to achieve the typical waxes. However, such polymerization conditions cause substantial olefin losses by hydrogenation to alkanes and reduced catalyst activity, which causes high residual ash contents in the product. Particularly high chlorine and titanium contents require costly purification steps.

The production of 1-olefin polymer waxes with narrow molecular weight distribution and high isotacticity using metallocene catalysts is known (see EP 321 852). For many uses of waxes, the high isotaxis and hardness of these products, which results in high melting heats higher than 80 J / g for polypropylene waxes, is disadvantageous.

The production of 1-olefininstereoblock polymer waxes (EP 321 853) using metallocene catalysts that reduce isotaxis by a large number of non-inert ions is known. The low activity of these catalyst systems and the impossibility of regulating isotaxis are disadvantageous.

Further, it is known to produce polyolefin waxes with different isotaxies by varying the polymerization temperature (see EP 416 566). However, it is disadvantageous that the activity of the catalysts decreases strongly with the polymerization temperature and that the achievable molecular weights are low and not adjustable independently of isotaxis.

It is further known that crystallinity can be reduced by copolymerization (EP 384 264). It is disadvantageous here to reduce the melting point of the copolymer to the melting point of the homopolymer, which limits the field of application.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to provide a polyolefin wax which avoids the disadvantages of the prior art and in particular has a reduced isotaxis and hardness at the same high melting point.

Accordingly, the present invention provides a polyolefin wax with a melt viscosity of 0.1 to 100000 mPa · s, preferably 1 to 60000 mPa · s, particularly preferably 50 to 60000 mPa · s at 170 ° C, a DSC with a melting heat of less than 80 J / g DSC with a melting point greater than 130 ° C and a molecular weight distribution Mw / Mn less than or equal to 3. Polypropylene waxes are preferred.

The polyolefin waxes of the present invention can be extracted with at least 10% by weight diethyl ether. A possibility for determining the isotaxy of crystalline polyolefin waxes is the solvent extraction method in a Soxleth extractor, while the highly crystalline isotactic fractions remain undissolved in the residue. The ether extracted portion corresponds to the atactic proportions of the polyolefin wax.

The present invention further provides a process for producing polyolefin waxes having a melt viscosity of 50 to 100,000 mPa.s at 170 ° C, a DSC melting point below 80 J / g, a DSC melting point above 130 ° C and a molecular weight distribution Mw / Mn lower. or equal to 3, in the presence of a catalyst comprising a stereorigid metallocene compound A and a cocatalyst B, wherein the metallocene compound A is used as a rac / meso form mixture in a rac / meso ratio of < 0.5.

In the racemic form (rac-form) of the stereorigid metallocene compound A, the two enantiomers can only be converted by reflection. In the meso-form, the image and the mirror image are mutually convertible by rotation. The term meso-form is also understood to mean that in a variety of metallocene ligands, such as dimethylsilyl (2-methyl-indenyl) (indenyl) ZrCl2, a second pair of enantiomers is formed in which the more voluminous portions of the two ligand systems are superimposed.

Thus, the following compounds (b) and (c) represent the rac form and compounds (a) and (d) represent the meso form

X = R 'is a compound of formula I

The stereorigid metallocene compound A is preferably a metallocene of formula I

in which

M ¹ denotes titanium, zirconium, hafniur, vanadium, niobium or tantalum,

R ^1, R ^2, R ^3, R ⁴ and R ⁵ are identical or different and denote hydrogen, alkyl having 1 to 20 carbon atoms, aryl having 6 to 14 carbon atoms, alkoxy having 1 to 10 carbon atoms, (C 2 -C 10) alkenyl, (C 7 -C 20) arylalkyl, (C 7 -C 20) alkylaryl, (C 6 -C 10) aryloxy, (C 1 -C 10) fluoroalkyl,

A (C 6 -C 10) haloaryl group, a (C 2 -C 10) alkynyl group, which is -S (R 6) ₃ , which is an alkyl group of up to 10 carbon atoms, a halogen atom or a 5-6 membered heteroaromatic radical which it may contain one or more heteroatoms; to r 4 form one or more rings with the connecting atoms,

R is a residue

whereas

O

M denotes carbon, silicon, germanium or tin,

9

R and R are the same or different and represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to carbon atoms, an aralkyl group having 7 to 10 carbon atoms; up to 20 carbon atoms, 7 to 20 carbon atom alkylaryl, 6 to 10 carbon atom aryloxy, 1 to 10 carbon atom fluoroalkyl, 6 to 10 carbon atom haloaryl or 2 to 10 carbon atom alkynyl, or r8 and form together with the atom connecting them a ring and p denotes 0, 1, 2 or 3 and r10 and rH are the same or different and denote a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms atoms, aryl of 6 to 10 carbon atoms, aryloxy of 6 to 10 carbon atoms, alkenyl of 2 to 10 carbon atoms, arylalkyl of 7 C 7 -C 40 alkylaryl, C 8 -C 40 arylalkenyl, hydroxy or halogen.

Preferred are compounds of the formula I in which zirconium or hafnium, especially zirconium, R 1, R 1, R 2 and R 4 are the same or different and denote a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 6 carbon atoms. up to 10 carbon atoms, 1 to 4 carbon alkoxy, 2 to 6 carbon alkenyl, 1 to 6 carbon fluorine, 1 to 6 carbon halogen, or 5 or 6 ring heteroaromatic radicals, which may contain one or more heteroatoms, or adjacent radicals R ¹ to R ⁴ form together with the atoms joining them, a ring, r ⁵ denotes an alkyl group having 1 to 10 carbon atoms,

O

M represents a carbon or silicon atom, especially silicon, and n

R c and R c are the same or different and are hydrogen, C 1 -C 6 alkyl, C 6 -C 10 aryl, C 1 -C 6 alkoxy, C 2 -C 4 alkenyl, arylalkyl (C 7 -C 10) or C 7 -C 10 arylalkyl; or

Q Q

R c and R c together with the atom connecting them form a ring, p is 1 or 2, preferably 1 and

R ^-a and RH are the same or different and denote a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, in particular a methyl group, an alkoxy group having 1 to 3 carbon atoms, an aryl group having 6 to 8 carbon atoms, an aryloxy group having 6 to 8 C 2 -C 4 alkenyl, C 7 -C 10 arylalkyl, C 7 -C 10 alkylaryl, C 8 -C 12 arylalkenyl or halogen, preferably chlorine.

Examples of metallocene components of the catalyst system of the present invention include the raca meso-forms of the following metallocene compounds:

dimethylsilandiyl-bis- (indenyl) -zirconium dichloride dimethylsilandiyl-bis- (tetrahydroindenyl) -zirconium dichloride dimethylsilandiyl-bis- (4-naphthyl-indenyl) -zirconium dimethylsilandiyl-bis- (2-methyl-benzoindenyl) -zirconium-dichloride dimethyl-indenyl) zirconium dimethylsilandiyl-bis- (2-methyl-tetrahydroindenyl) -zirconium dimethylsilandiyl-bis- (2-methyl-4- (1-naphthyl) -indenyl) zirconium dimethylsilandiyl-bis- (2-methyl- 4- (2-naphthyl) -indenyl) zirconium dimethylsilandiyl-bis- (2-methyl-4-phenyl-indenyl) -zirconium dimethylsilandiyl-bis- (2-methyl-4-tert-butyl-indenyl) zirconium dimethylsilandiyl -bis- (2-methyl-4-isopropyl-indenyl) -zirconium dimethylsilandiyl-bis- (2-methyl-4-ethyl-indenyl) -zirconium dimethylsilandiyl-bis- (2-methyl-4-α-acenaphth-indenyl) -bis- dimethylsilandiyl-bis- (2,4-dimethyl-indenyl) -dimethylsilandiyl-bis- (2-ethyl-indenyl) -zirconium dichloride dimethylsilandiyl-bis- (2-ethyl-4-ethyl-indenyl) -zirconium dichloride dimethylsilandiyl-bis- (2-ethyl-4-phenyl-indenyl) zirconium dichloride dimethylsilandiyl-bis- (2-methyl-4,5-benzo-indenyl) Dimethylsilandiyl-bis- (2-methyl-4,6-diisopropyl-indenyl) zirconium dichloride dimethylsilandiyl-bis- (2-methyl-4,5-diisopropyl-indenyl) zirconium dichloride zirconium dichloride

Dimexhylsilandiyl-bis- (2,4,6-trimethyl-indenyl) -dimethylsilandiyl-bis- (2,5,6-xrimexyl-indenyl) -zirconium dichloro-dimethyl- bis- (2,4,6-trimethyl-indenyl) Dimethylsilandiyl-bis- (2-methyl-5-isobuxyl-indenyl) -zirconium dichloride Dimethylsilandiyl-bis- (2-methyl-5-x-buxyl-indenyl) methyl (phenyl) silandiyl-bis- (2-methyl-zirconium dichloride) zirconium dichloride Methyl (phenyl) silandiyl-bis- (2-methyl-4,6-diisopropyl-indenyl) -zirconium methyl (phenyl) silandiyl-bis- (2-methyl-4-isopropyl-indenyl) -4-phenyl-indenyl) zirconium dichloride Methyl (phenyl) silandiyl-bis- (2-methyl-4,5-benzo-indenyl) -zirconium dichloride methyl (phenyl) silandiyl-bis- (2-methyl-4,5- (methylbenzo) -indenyl) zirconium dichloride methyl (phenyl) silandiyl-bis- (2-methyl-4,5- (tetramethylbenzo) indenyl) -zirconium methyl (phenyl) silandiyl bis- (2-methyl-4-aacenaphthalenyl) zirconium methyl (phenyl) silandiyl zirconium dichloride -bis- (2-methyl-indenyl) -zirconium di10 methyl (phenyl) silandiyl-bis- (2-methyl) chloride 1-5-isobutyl-indenyl) zirconium dichloride

1,2-ethanediyl-bis- (2-methyl-4-phenyl-indenyl) zirconium dichloride

1,2-ethanediyl-bis- (2-methyl-tetrahydroindenyl) zirconium dichloride

1,2-ethanediyl-bis- (tetrahydroindenyl) zirconium dichloride

1,4-Butanediyl-bis- (2-methyl-4-phenyl-indenyl) -zirconium dichloride

1,2-ethanediyl-bis- (2-methyl-4,6-diisopropyl-indenyl) zirconium dichloride

1,4-Butanediyl-bis- (2-methyl-4-isopropyl-indenyl) zirconium dichloride

1,4-Butanediyl-bis- (2-methyl-4,5-benzo-indenyl) zirconium dichloride

1,2-ethanediyl-bis- (2-methyl-4,5-benzo-indenyl) zirconium dichloride

1,2-ethanediyl-bis- (2,4,7-trimethyl-indenyl) -zirconium dichloride

1,2-ethanediyl-bis- (2-methyl-indenyl) zirconium dichloride

1,4-butanediyl-bis- (2-methyl-indenyl) zirconium dichloride as well as dialkyl derivatives of the above-mentioned metallocenes, such as:

dimethylsilandiyl-bis- (indenyl) -zirconium dimethyl dimethylsilandiyl-bis- (tetrahydroindenyl) -zirconium diethyl dimethylsilandiyl-bis- (2-methylbenzo-indenyl) -zirconium dimethylsilandiyl-bis- (2-methyl-indenyl) zirconium dibutyl or also monoalkyldibutyl monoalkylates , for example :

dimethylsilandiyl-bis- (indenyl) -zirconium chlorraethyl dimethylsilandiyl-bis- (xetrahydroindenyl) -zirconium chlorexethyl dimexethylsilandiyl-bis- (2-mexobenzenzo-indenyl) -zirconium chloromethyl dimexhylsilandiyl-bis- (2-methyl-indenyl) -butirium

The rac-forms and meso-forms of the following metallocene compounds are particularly preferred:

dimethylsilandiyl-bis- (2-methyl-4-a-acenaphth-indenyl) -zirconium dichloride dimethylsilandiyl-bis- (2-ethyl-4-phenyl-indenyl) -zirconium dichloride.

The rac-forms and meso-forms of the following metallocene compounds are particularly suitable:

diraethylsilyl- (2-methyl-4,5-benzoindenyl) 2ZrCl ₂ dimethylsilyl- (2-methyl-indenyl) 2ZrCl ₂ dimethylsilyl- (2-methyl-indenyl) (2-methyl-4,5-benzoindenyl) ZrCl ₂ dimethylsilyl- (2-methyl-4-phenyl-indenyl) ₂ ZrCl ₂ dimethylsilyl- (2-methyl-indenyl) (2-methyl-4-phenyl-indenyl) ZrCl 2 dimethylsilyl- (2-methyl-4,6-diisopropyl-indenyl) ₂ ZrCl ₂ dimethylsilyl- (2,5,6-trimethyl-indenyl) ₂ ZrCl ₂ and dimethylsilyl- (2-methyl-4-naphthyl-indenyl) ₂ ZrCl ₂ ·

In the synthesis of the metallocene compound A used in the process of the present invention, the ratio of rac form to meso form directly after metallocene synthesis is usually 2: 1 to 0.5: 1. However, the desired corresponding form of metallocene can be enriched by crystallization and the ratio of rac-form to meso-form can be arbitrarily adjusted.

Another possibility to adjust the rac-form / meso-form ratio is to add, for example, the meso-form of the metallocene to the rac / meso 1: 1 mixture from the synthesis. The enriched meso-form of metallocenes is produced in larger quantities in the production of rac-metallocenes for the production of highly isotactic polyolefin molding compositions.

In principle, any compound which, by virtue of its Lewis acidity, can convert a neutral metallocene into a cation and stabilize it (labile coordination) is suitable as cocatalyst B in the process according to the invention. In addition, the cocatalyst or anion formed therefrom should not enter any further reaction with the formed metallocene cation (EP 427 697). An aluminum compound and / or a boron compound is preferably used as the cocatalyst.

The boron compounds preferably have the formulas R ¹² _x NH _{4 x} BR ¹³ 4, R ¹² _x PH _{4 x} BR ¹³ 4, R ¹² 3CBR ¹³ 4 or BR ¹³ 3, wherein x denotes a number from 1 to 4, preferably 3.

9

R are the same or different, preferably the same, and denotes an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 18 carbon atoms, or two radicals R together with the connecting atoms form a ring and

R ¹³ are the same or different, preferably the same, and denotes an aryl group having 6 to 18 carbon atoms which may be substituted by an alkyl group, a haloalkyl group or fluorine.

In particular, R ^ represents an ethyl group, propyl

Ar 13 'or a phenyl group and R a phenyl, pentafluorophenyl, 3,5-bistrifluoromethylphenyl, mesityl, xylyl or tolyl group (EP 277 003, EP 277 004 and EP 426 638).

Preferably, an aluminum compound such as an aluminoxane and / or an aluminum alkyl is used as the cocatalyst.

Aluminoxane is particularly preferably used as the cocatalyst, in particular of formula IIIa for the linear type and / or formula IIb for the cyclic type

A I — 0A I — 0 — A (Ha)

R

AND

A 1-0 (IIb) wherein in formulas IIIa and IIb the radicals are the same or different and denote a hydrocarbon group having 1 to 20 carbon atoms, such as an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or benzyl and p denote an integer of 2 to 50, preferably 10 to 35.

Preferably, the radicals R @ ⁴ = ^{4 are the} same and denote a hydrogen atom, a methyl group, an isobutyl group, a phenyl group or a benzyl group, particularly preferably a methyl group.

If the radicals are different, it is preferably a methyl group and a hydrogen atom, or alternatively a methyl and isobutyl group, the hydrogen atom or the isobutyl group being present in a numerical fraction of 0.01 to 40% (radical R1).

Methods for producing aluminoxanes are known (see for example DE 4 004 477).

The exact spatial structure of aluminoxanes is unknown (J. Am. Chem. Soc. (1993) 115, 4971). For example, it is possible that chains and rings join into larger two-dimensional or three-dimensional structures.

Irrespective of the type of production, the variable content of the unreacted starting aluminum compound, which is present in free form or as an adduct, is common to all aluminoxane solutions.

It is also possible to pre-activate the metallocene compound of the present invention before use in the polymerization reaction by means of a cocatalyst, in particular alurainoxane. As a result, the polymerization activity is clearly increased. The pre-activation of the metallocene compound is preferably carried out in solution. The metallocene compound is preferably dissolved in a solution of the aluminoxane in an inert hydrocarbon. Suitable inert hydrocarbons are aliphatic or aromatic hydrocarbons, toluene being preferred.

The concentration of the aluminoxane in the solution is in the range of about 1% by weight to the saturation limit, preferably 5 to 30% by weight, in each case based on the amount of the total solution. The metallocene can be used in the same concentration but is preferably used in an amount of 10 ^{"4 to} 1 mol per mol alurainoxanu. The pre-activation time is 5 minutes to 60 hours, preferably 5 to 60 minutes. The process is carried out at a temperature of -78 ° C to 100 ° C, preferably 0 ° C to 70 ° C.

The metallocene compound is preferably used in this case at a concentration of from 3 to 8, based on the transition metal, of from 10 to 10%, preferably from 10 to 10 mol of transition metal, for 1 day solvent or 1 dm reactor volume. The aluminoxane is preferably used in a concentration of 10 to 10 mol, preferably 10 to 10 mol, for 1 dm of solvent or for 1 dm of reactor volume. The other cocatalysts are used in about equimolar amounts to the metallocene compound. In principle, however, higher concentrations are also possible.

Preferably, in the process of the present invention, the metallocene compound is reacted with the cocatalyst outside the polymerization reactor in a separate step using a separate solvent. A carrier may be used.

In the process of the present invention, a prepolyraeration can be performed with the aid of a metallocene compound. For prepolymerization, the olefin used for the polymerization or one of the olefins used for the reaction is preferably used.

The stereorigid metallocene compound A used in the process of the present invention is preferably reacted with cocatalyst B using a suitable solvent outside the polymerization reactor in a separate step. A carrier may be used. To this end, the metallocene compound can first be reacted with a carrier and then with a cocatalyst. However, the cocatalyst may also first be coupled to a support and then reacted with the metallocene compound. It is also possible to carry the reaction product of a metallocene compound and a cocatalyst. In these carrier reactions, the ratio of rac-form to meso-form of metallocene remains unchanged due to similar chemical properties. Suitable carrier materials are, for example, silica gels, aluminum oxides or other inorganic carriers such as magnesium chloride or graphite. The supported cocatalyst can be prepared, for example, as described in EP 567 952. A suitable carrier material is also a pulverulent polymer such as that described in EP 563 917.

The catalyst can be dosed as a solution, as a suspension or in a dry form in a supported form. Hydrocarbons, such as toluene, heptane, hexane, pentane, butane or propane, as well as technical petroleum fractions, are generally suitable as solvents or suspending agents for the catalyst or cocatalyst.

The polyolefin wax of the present invention is suitable for wide η because of the wide hardness adjustment

application as, for example, as a recipe component in high hardness toners, or as a matrix for pigment preparations, as a processing aid for plastics and as a hotmelt for lower hardness products.

By means of this process, polyolefin waxes with a narrow molecular weight distribution are smaller

A * than 3. When enriching the atactic fraction by extracting the total sample with ether, the GPC spectrum of the low isotactic fraction, extractable by ether, is virtually identical to the GPC of the total sample.

The process according to the invention can be carried out in solution, in suspension or in the gas phase at a temperature in the range of 40 to 120 ° C, at an olefin partial pressure of 0.1 to 5.0 MPa, at a hydrogen partial pressure of 0 to 1.0 MPa, with an addition (based on Al) of 0.01 to 10 mmol of cocatalyst per liter of suspending agent and with a catalyst / cocatalyst ratio of 1: 1 to 1: 1000.

In the process of the present invention, olefins of formula R ^and CH = CHR 4 are preferably polymerized, wherein R ^a and R 4 are the same or different and denote a hydrogen atom or an alkyl radical of 1 to 28 carbon atoms, or R ^a and R 6 form with them. linking carbon atoms one or more rings. Examples of such olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, norbornene or norbornadiene. Propylene is preferred.

For the polymerization, additional organoaluminum compound C, such as trimethylaluminum, triethylaluminum, triisobu18 tylaluminium or isoprenylaluminium, may additionally be added prior to the addition of the catalyst to advertise the polymerization system at a concentration of 1 to 0.001 mmol Al for 1 dm 2 of reactor volume.

The polymerization can be carried out discontinuously or continuously, in one or more stages, and any delay times can be realized with only a slight reduction in the time-dependent polymerization activity.

The molecular weight of the waxes of the present invention can be controlled by hydrogen in relation to the desired melt viscosity. Thus, the melt viscosities of polypropylene waxes, measured at 170 ° C, are in the range of 50 to 100,000 mpa.s. In addition, the polymerization temperature can be varied to control the molecular weight.

The polyolefin waxes of the present invention are particularly suitable as additives, for example for synthetic materials.

DETAILED DESCRIPTION OF THE INVENTION

Melting points and melting points were determined by DSC measurement at a heating and cooling rate of 20 ° C / min from the second heating. The melt viscosity is determined at 170 ° C using a rotary viscometer.

The IR-isotaxy assay is performed according to J. P. Luong, J. Appl. Polym. Chem., 3,302 (1960).

The sliding hardness is determined by the ball pressure method described in the uniform methods

Deutschen Gesellschaft Fettchemie (DGF) under M-III 9a (57).

Example 1

The inert reactor of 100 dm @ 2 as described in EP 602 509 is charged with 30 kg of propene and 42 mmol of triethylaluminum and is heated to 60 DEG C. with stirring at 170 rpm and hydrogen is metered in at 0.05. MPa.

In parallel to this, 30 mg of dimethylsilyl-bis-2-methylbenzoindenylzirconium dichloride with a rac / meso ratio of 1: 8 was dissolved in 100 ml of a toluene solution of methylaluminoxane and stirred for 15 minutes.

The polymerization is started by pumping the catalyst solution in 20 minutes. By controlling the cooling, the internal temperature of the reactor is allowed to rise to 70 ° C. Hydrogen is metered in and kept constant by 1.5% v / v by gas chromatography control. After one hour, the polymerization was terminated with carbon dioxide and the slurry was melted after propylene was distilled off. 7.0 kg of polypropylene wax having a melt viscosity at 170 DEG C. of 1800 mPa.s are obtained. The characteristic values are given in Table 1.

Example 2

The procedure of Example 1 was carried out with 16 mg of the same metallocene at a ratio rac / meso = 1: 6. The yield is 5.67 kg. Characteristic values are given in Table 1.

Example 3

The procedure of Example 1 was carried out with 15.3 mg of the same metallocene at a ratio rac / meso = 1: 6. The yield is

6.6 kg. Characteristic values are given in Table 1.

Example 4

The procedure of Example 1 was carried out with 15 mg of the same metallocene at a ratio rac / meso = 1: 2.7 using 2.8 vol% hydrogen. Yield 6.6 kg. Characteristic values are given in Table 1.

Example I (comparative)

The procedure of Example 1 was followed by a metallocene at a rac / meso ratio of 8.5 kg. Characteristic values are performed with s = 12: 1.

mg the sameThe yield is given in Table 1.

Table 1

Example 1 2 3 4 AND rac / meso 1/8 1/6 1 / 2,9 1 / 2.7 12/1 kg / mg cat. 0.23 0.35 0.43 0.77 0.85 melt viscosity (mPa.s) 1800 1740 1500 282 1910 TI (° C) 145 147 142 144 144 heat melting (J / g) 48 52 68 77 107 IR-isotactic index 48% 62 61% 78% 92% sliding hardness (bar) 180 223 560 810 > 1000 etherem extracted readable (%) 47 37 14 3 Mn (g / mol) 8810 9065 4180 9085 Mw / Mn 2.5 2.4 2.8 2.5 Mn ether extract 11300 11200 11300 Mw / Mn 2.5 2.5 2.5

Example 5

The procedure of Example 1 was carried out with 65 mg of dimethylsilyl-bis- (2-methylindenyl) zirconichloride at a rac / meso ratio of 1: 5 and tegulation with 1.5% by volume of hydrogen. Yield 6.8 kg. Characteristic values are given in Table 2.

Example II (comparative)

The procedure of Example 5 was carried out with 22 mg of the same 22 metallocene at a ratio rac / meso = 1: 1. Yield 6.8 kg. Characteristic values are given in Table 2.

Example 6

The procedure of Example 1 was carried out with 70 mg of dimethylsilyl- (2-methylindenyl) (2-methyl-4,5-benzoindenyl) zirconichloride at a rac / meso ratio of 1: 6 and tegulation with 1% hydrogen by volume. Yield 10.4 kg. Characteristic values are given in Table 2.

Example III (comparative)

The procedure of Example 6 was carried out with 25 mg of the same metallocene at a ratio rac / meso = 1: 1. Yield 7.4 kg. Characteristic values are given in Table 2.

Example 7

The procedure of Example 1 is carried out with 21.6 mg of dimethylsilyl- (2-methyl-4-phenylindenyl) zirconichloride at a rac / meso ratio of 1: 5.6 and a tegulation of 9.2% by volume of hydrogen. Yield 6.5 kg. Characteristic values are given in Table 2.

Example IV (comparative)

The procedure of Example 7 was carried out with 20 mg of the same metallocene at a ratio rac / meso = 1: 1. The yield is

9,6 kg. Characteristic values are given in Table 2.

Table 2

Example 5 II 6 III 7 IV rac / meso 1/5 1/1 1/6 1/1 1 / 5,6 1/1 kg / mg cat. 0.104 0,691 0.149 0.296 0.3 0.48 melt viscosity (mPa.s) 2300 3180 1830 2000 2266 1410 Tm (° C) 140 140 138 138 157 152 heat of melting (J / g) 75 125 70 107 76 110 IR-isotactic index 77% 86% 72% 83% 79% 91% sliding hardness (bar) 910 > 1000 810 > 1000 817 > 1000 etherem extracted readable (%) 12.5 16.2 Mn (g / mol) 11600 9400 Mw / Mn 2.5 2.4 Mn ether extract 8430 7330 Mw / Mn 2.6 2.9

Example V (comparative)

A comparative example of Example 3 in DE 31 48 229 is worked out. A polypropylene wax is obtained with the following properties.

melt viscosity (mPa.s) 1810

Tm (° C) 145.5 melting heat (J / g) 35

IR-isotactic index 70% sliding hardness (bar) 510

extractable with ether (96) 39 Mn (g / mol) 2600 Mw / Mn 6.9 Mn ether extract 1570 Mw / Mn 4.6 Mn extraction residue 5280 Mw / Mn - 5.5

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Claims (2)

PATENT CLAIMS Polypropylene wax having a melt viscosity of 50 to 100000 mPa.s at 170 ° C, a DSC with a melting point of less than 80 J / g, a DSC with a melting point of greater than 130 ° C and a molecular weight distribution Mw / Mn less than or equal to 3. 2. A process for producing polyolefin waxes having a melt viscosity of 50 to 100000 mPa.s at 170 ° C, a DSC with a melting point of less than 80 J / g, a DSC with a melting point of greater than 130 ° C and a molecular weight distribution Mw / Mn of less than or equal to 3. , in the presence of a catalyst comprising a metallocene compound A and a cocatalyst B, wherein the metallocene compound A is used as a mixture of rac form and meso form in a ratio rac / meso = <0.5.